Interpolymers of carbon monoxide and method for preparing the same



Patented Jan. 24, 1950 INTERPOLYMERS OF CARBON MONOXIDE AND METHOD FORPREPARING THE SAME Merlin M. Brubaker, Chadds Ford, Pa., assignor to E.I. du Pont de Nemours and Company, Wilmington, Del., a corporation ofDelaware No Drawing. Application June 8, 1949, Serial No. 97,908

15 Claims. 1

This invention relates to new polymers and to methods for theirpreparation. The present application is a continuation-in-part of mycopending application, S. N. 552,374, filed September 1, 1944, which inturn is a continuation-inpart of my earlier applications. N. 449,765,filed July 4, 1942, both now abandoned. In the said applications I havedisclosed the interpolymerization of carbon monoxide with unsaturatedsubstances, such as aliphatic monoolefines, fluorinated ethylenes, vinyland vinylidene compounds.

The use of carbon monoxide as a reagent in the manufacture of organiccompounds has long been known in the art. It has been employed in theproduction of hydrocarbons, alcohols, and esters by treatment withhydrogen in the presence .of selected metallic catalysts. Acids andesters have been prepared by treating alcohols or alcoholates withcarbon monoxide, and aldehydes and ketones have been synthesized bycausing hydrocarbons to react with carbon monoxmore specific object toprovide new polymers of carbon monoxide with polymerizable organiccompounds containing ethylenic unsaturation. Another object is toprovide orientable carbon monoxide interpolymers characterized by hightensile strength, superior film and fiber-forming properties, and highintrinsic viscosity. It is a still further object to provide a simpledirect process for obtaining such polymers. Other objects will appearhereinafter.

According to this invention, a process'is provided for converting carbonmonoxide and other monomers into polymeric materials of high qualityincluding orientable solid polymers. embodiment, carbon monoxide ispolymerized with polymerizable organic compounds containing ethylenicunsaturation, in the presence of a peroxy catalyst and in the absence ofa Friedel- Crafts catalyst, to yield normally solid carbonyl In onegroup-containing polymers. In the preferred mode of operation, thepolymerizable organic compounds and carbon monoxide are heated togetherunder pressure in the presence of an organic peroxide catalyst and inthe absence of a Friedel-Crafts catalyst. The polymerization can becarried out either as a batch, semi-continuous, or continuous operation.It is. generally conducted in vessels which are either constructed of orlined with glass, stainless steel, silver, etc.

By polymerizable organic compounds containing ethylenic unsaturation ismeant compounds which contain the group C=C and which, in accordancewith the present state of the art, are recognized as being capable ofundergoing a polymerization reaction involving addition across theethlyenic double bond, which reaction is catalyzed by peroxy compounds.

The polymerizable organic compounds used in the practice of thisinvention include any organic compound containing ethylenic unsaturationand capable of being polymerized through the ethylenic double bond. Aclass of these compounds which, as the art has now developed, iscognizable under the term peroxide-polymerizable embraces aliphaticmonoolefines; ethylene; propylene; the butylenes; butadiene; vinyl andvinylidene compounds; fiuorinated ethylenes; i. e., vinyl fluoride,vinylidene fluoride, trifiuoroethylene and tetrafiuoroethylene; vinylchloride; vinylidene chloride; organic vinyl esters such as vinylpropionate, vinyl benzoate, vinyl acetate, vinyl isobutyrate, vinyllaurate, etc.; vinyl ketones such as methyl vinyl ketone and methylisopropenyl ketone; styrene; acrylic and methacrylic acids and theirderivatives such as esters, nitriles, and anhydrides; diallyl compoundssuch as diallyl phthalate; butenedioic acids and their derivatives, suchas maleic and fumaric acids, their esters, nitriles and anhydrides, andthe like. Combinations of ethylene with one or more additionalpolymerizable organic compounds are particularly useful forpolymerization with carbon monoxide in the practice of this invention.Organic compounds which contain at'least one terminal methylene groupare preferred for polymerization with carbon monoxide in the practice ofthis invention since the most satisfactory results with respect to yieldand polymer quality are obtained when such compounds are used.

As catalysts for use in this invention, any peroxy compound can be used.Within the scope of the term "peroxy compound is meant to be includedanycompound which is capable of in- I ducing vinyl polymerization and whichcontains the bivalent group, -O-O--. Examples of such compounds areoxygen, benzoyl peroxide, lauroyl peroxide, succinoyl peroxide,diphthalic acid peroxide, dioxan peroxide, diethyl dioxide, peraceticacid, perbenzoic acid, potassium peroxydisulfate, ammoniumperoxydisulfate, sodium and potassium percarbonates, and the like. Otheroperable catalysts are azines such as diphenylketazine and benzalazine,and organo lead compounds such as diethyl lead dibromide. In general,compounds which readily form free radicals under the polymerizationconditions may be employed as catalysts.

The concentration of catalysts required in the practice of thisinvention may vary over a wide range. For reasons of economy and inorder to obtain products of relatively high molecular weight, however,it is generally desirable to use low concentrations of catalysts, forexample, from about 0.01% to about 1%, based on the amount ofpolymerizable monomers. Lower molecular weight products may be desirablefor many uses, and these are conveniently prepared with catalystconcentrations up to 15% or more.

Although use of an added reaction medium is not essential tooperability, a liquid is usually added to serve as a reaction medium. Asreaction media for selected polymerizations there can be used water orany non-polymerizable, normally liquid, preferably volatile organiccompound of the following classes: hydrocarbons, halogenatedhydrocarbons, alcohols, ethers, esters, ketones, or nitroparafl'ins.Specific examples are benzene, isooctane, cyclohexane, dioxan, tertiarybutyl alcohol, methyl formate, tetraethyl silicate, carbontetrachloride, acetone, nitromethane, etc. Of these, anhydrous,thiophene-free benzene is preferable for use in polymerizationsinvolving both carbon monoxide and ethylene because of its inertness.Mixtures of two or more such materials can sometimes be employedadvantageously. Some of the added reaction media may also function asreactants and, as such, may exert a profound influence on the nature ofthe resulting polymer. Thus, the choice of reaction medium usuallydepends upon the nature of the materials to be polymerized with carbonmonoxide and the type of polymer desired. Since water, even in minoramounts, usually has an adverse efiect on the polymerization of carbonmonoxide with ethylene, the organic reaction media used inpolymerizations involving both carbon monoxide and ethylene arepreferably carefully dried before use.

It should be noted that in the polymerization of carbon monoxide withvinyl chloride the pH ofthe reaction mixture should be maintained,preferably, on the acid side throughout the reaction. Similarly, in thecase of tetrafiuoroethylene, it is preferable to operate at a pH ofabout 3, which is obtained by adjusting the pH of the original chargewith an acid such as formic acid. With respect to the polymerization ofcarbon monoxide with acrylonitrile, it has been found that a hydrohalicacid such, preferably, as hydrochloric acid, should be present in suchan amount as to produce a pH of 1 or less. Furthermore, it is desirableto employ concentrations not exceeding 20% of hydrochloric acid becauseat higher concentrations of acid the acrylonitrile tends to hydrolyzewith sacri- H06 in yield of polymer.

For best results reactants and any added liquid reaction media arecarefully purified before use. Although oxygen is an operable catalystin this invention, it usually has a deleterious effect inpolymerizatlons involving use of another peroxy compound as catalyst.Therefore, oxygen is preferably excluded from the reaction vessel duringpolymerization. The process of this invention is operable when thegaseous reactants con tain 200 or more parts of oxygen per million partsof reactant, but it is desirable and not unduly troublesome andexpensive to hold the oxygen concentration below 20 parts per million.Water is usually likewise undesirable in polymerizations involvingcarbon monoxide and ethylene. It may be conveniently removed from thesereactants by passing them through a bed of activated alumina.

Carbon monoxide for use in the process of this invention may be obtainedfrom any source, for example, by the action of steam or carbon dioxideon hot coal, by the reaction of methane with steam, or by thedecomposition of formic acid or methyl formate. It is preferably free ofmetal carbonyls such as iron carbonyl, nickel carbonyl, and coppercarbonyl. In order to insure uniformity of polymer composition, carbonmonoxide introduced into the recation vessel during the polymerizationreaction is preferably introduced simultaneously with the other polymeringredients in a definite predetermined ratio.

The process of this invention may be carried out at temperatures varyingfrom 25 C. to as high as 350 C. or higher. The optimum temperature ineach case depends upon the nature of the materials to be polymerized,the reaction medium, the catalyst, the pressure, and the type of polymerdesired. If products of maximum molecular weight are desired it isusually desirable to operate at the lowest temperatures possibleconsistent with a reasonable reaction rate. Use of higher temperaturesusually leads to lower molecular weight products which arelower-softening and more soluble. In most cases the preferredtemperature is between 50 and 250 C. Optimum temperatures can readily bedetermined for each polymerization system by carrying out a fewpreliminary experiments.

The molecular weight of the polymers of this invention is also afunction of the pressure used in their preparation; increased pressureusually leads to products of higher molecular Weight. The polymerizationcan be carried out at superatmospheric pressures. Pressures ranging fromatmospheric to 3000 atmospheres and above may be used, depending uponthe reactants, catalysts, reaction media, temperature, and mechanicallimitations of the equipment. It is generally preferred to operate atpressures within the range of from 20 to 1500 atmospheres. Thus, thenormally solid etlilylene/carbon monoxide polymers are most convenientlyprepared at pressures of about 500 to 1000 atmospheres.

The following examples illustrate the practice of this invention anddemonstrate operable conditions. Parts given are by weight unlessotherwise specified. The pressure reaction vessel used in each exampleis lined with silver, although reaction vessels made of or lined withany other inert material may be employed, as desired. In each caseunless otherwise specified, the reactor is flushed with oxygen-freenitrogen to displace atmospheric oxygen immediately before the catalyst,reaction medium, and reactants are added.

Example 1.'I'his example illustrates the benzoyl peroxide-catalyzedpolymerization of carbon monoxide and ethylene in water.

A pressure reaction vessel is charged with 0.5 part of benzoyl peroxideand 125 parts of water, closed, evacuated, pressured to 325 atmosphereswith carbon monoxide, and then further pressured to 500 atmospheres withethylene. The temperature of the agitated reaction mixture is raised to115 C. and maintained at 114 to 116 C. for a period of 11 hours duringwhich the pressure is kept at 920 to 940 atmospheres by occasionalrepressuring with ethylene. The vessel is cooled, the excess gases arebled off, and the vessel is opened. The polymer is isolated byfiltration and dried. There is thus obtained 0.25 part of a polymerhaving a melting point of 200 to 202 C. and giving a positive color testfor keto groups with meta-dinitrobenzene and alcoholic potassiumhydroxide (Biochem. J. 32, 1312 (1938)). The mol ratio of ethylene tocarbon monoxide in the polymer is 12:1. The polymer is soluble indimethyl formamide and insoluble in toluene, methanol, acetone, andacetic acid.

Example 2.This example illustrates the benzoyl peroxide-catalyzedpolymerization of carbon monoxide and ethylene in the absence of anadded reaction medium.

A pressure reaction vessel is charged with 0.5 part of benzoyl peroxide,closed, evacuated, and pressured to 700 atmospheres with a mixture ofcarbon monoxide and ethylene which mixture contains 50% carbon monoxideby weight. The

temperature of the agitated reaction mixture is raised to 75 C. andmaintained at 73 to 77 C. for a period of 13 hours during which thepressure is kept at 860 to 1000 atmospheres by occasional repressuringwith the mixture of carbon monoxide and ethylene. The vessel is cooled,the excess gases are bled off, and the vessel is opened. There is thusobtained 18 parts of a white, finel divided polymer which melts to aclear liquid when dropped on a metal surface heated to 191 to 192 C. orhigher temperatures. Within two minutes the melt gels and the gelremains soft and rubbery until it is cooled, when it becomes hard andbrittle. The mol ratio of ethylene to carbon monoxide in the polymer is1.16:1. The polymer is slightly soluble in chloroform, hot dioxane, hotnitroethane, and hot pyridine. It becomes insoluble in these solventswhen it is heated at 130 C. for 16 hours or at 160 C. for 30 minutes.One

part of the polymer mixed intimately with one part of wood flour andmolded at 2000 lbs. per sq. inch and 160 C. for minutes forms a barwhich has an impact strength of 0.37 lbs. per inch of notch (Charpymethod, pages 67-70, Handbook of Plastics, Simonds and Ellis, D. VanNostrand and Co., N. Y. C., 1943) Example 3.-This example illustratesthe diethyl dioxide-catalyzed polymerization of carbon monoxide andethylene introduced into the reactor as a 70 mixture by weight, in theabsence of an added reaction medium.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxide,closed, and pressured to 350 atmospheres with a mixture of carbonmonoxide and ethylene which mixture contains 70% carbon monoxide byweight. The temperature of the agitated reaction mixture is raised to120 C. and maintained at 118 to 123 C. for a period of 14.5 hours duringwhich the pressure is kept at 700 to 775 atmospheres by occasionalrepressuring with the mixture of carbon monoxide and ethylene. Thevessel is cooled, the excess gases are bled off, and the vessel isopened. There is obtained parts of a white, finely divided polymer whichsoftens but does not appear to melt under ordinary pressures up to 250C. The mol ratio of v ethylene to carbon monoxide in the polymer is1.30:1. A film pressed from th po y between smooth surfaces at 180 C. istransparent and brittle and has a tensile strength of 2640 lbs. per sq.inch with an elongation at break of 14%. One part of the polymer mixedintimately with one part of wood flour and molded at 1000 lbs. per sq.inch and 170 C. for 3 minutes forms a bar which has an impact strengthof 0.50 ft. lb. per inch of notch (Charpy).

Example 4.This example illustrates the formation of a crystalline,orientable polymer from a 30:70 mixture of carbon monoxide and ethyleneby weight with diethyl dioxide as catalyst.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxide,closed, and pressured to 500 atmospheres with a mixture of carbonmonoxide and ethylene which mixture contains 30% carbon monoxide byweight. The temperature of the agitated reaction mixture is raised to130 C. and maintained at 129 to 131 C. for 14 hours during which timethe pressure is kept at 850 to 1000 atmospheres by occasionalrepressuring with the mixture of ethylene and carbon monoxide. Thevessel is cooled, the excess gases are bled off, and the vessel isopened. There is obtained 101 parts of fused tough polymer which softensbut does not appear to melt under ordinary'pressures u to 250 C. The molratio of ethylene to carbon monoxide in the polymer is 1.25:1. Theinfrared absorption spectrum of the polymer affords ample evidence ofthe presence of keto groups in the polymer. The polymer is highlyswelled by and partiall soluble in chloroform. It mills satisfactorilyon a Thropp rubber mill at to C. A sheet of the polymer removed from therubber rolls and rolled at 50 C. from its origina1 thickness of 25 to 30mils to, a thickness of 6 mils has i .a tensile strength of 2840 lbs.per sq. inch in the direction of roll, with an elongation at break of16%. X-ray diagrams of the transparent rolled film show that the polymerhas a crystalline structure and that the film is highly oriented in thedirection of roll. The film pressed from the polymer between smoothsurfaces at 160 C. is hazy and mottled in appearance. Its tensilestrength is 2020 lbs. per sq. inch with an elongation at break of 24%.Bars molded at C., either in compression or injection molding equipment,have a tensile strength of 2000 to 2500 lbs. per sq. inch. When thepolymer is milled for 10 to 1.5 minutes on tight, unheated rubber millrolls, it becomes completel and readily soluble in chloroform or hotdioxan. This soluble polymer has an intrinsic viscosity of 1.0(determined at 25 C. in chloroform at a concentration of 0.1 g.

er 100 ml. of solution; intrinsic viscosity is defined in U. S. Patent2,130,948).

Example 5.--This example illustrates the use of tertiary butylhydroperoxide as a catalyst for the polymerization of carbon monoxideand ethylene. I

A pressure reaction vessel is charged with 0.25 part of a 62.5% solutionof tertiary butyl hydropcroxide in tertiary butyl alcohol. closedgandpressured to 450 atmospheres with a mixture of carbon monoxide andethylene which mixture contains 20% carbon monoxide by weight. Thetemperature of the agitated reaction mixture is raised to 130 C. andkept at 129 to 132 C. for a period of 15 hours during which time thepressure is maintained at 850 to-1000 atmospheres. The vessel is cooled,the excess gases are bled off, andthe vessel is opened. There isobtained rubber rolls to remove the benzene.

42 parts of fused tough polymer with properties much like those of thepolymer obtained in Example 4. The mol ratio of ethylene to carbomonoxide in the polymer is 1.50:1.

Example 6.This example illustrates the polymerization of carbon monoxideand ethylene in isooctane to obtain a soluble polymer.

A pressure reaction vessel is charged with 0.5 port of diethyl dioxideand 100 parts of isooctane, closed, evacuated, and pressured to 450atmospheres with a mixture of carbon monoxide and ethylene which mixturecontains 10% carbon monoxide by weight. The temperature of the agitatedreaction mixture is raised to 131 C. and maintained at 128 to 132 C. fora period of 7.5 hours during which the pressure is kept at 840 to 1000atmospheres by occasional repressuling with the mixture of ethylene andcarbon monoxide. The vessel is cooled, the excess gases are bled off,and the vessel is opened. The'polymer is milled on hot rubber rolls toremove the isooctane. The yield of dry polymer is 59 parts. It melts at84 C. A film pressed at 80 C. between smooth surfaces is transparent andpliable and has a tensile strength of 960 lbs. per sq. inch with anelongation at break of 50%. The polymer is soluble in chloroform or hotdioxanand has an intrinsic viscosity of 0.39 (determined in dioxan at 85C. at a concentration of 0.1 g./100 ml. of solution). The mol ratio ofethylene to carbon monoxide in the polymer is 3.411.

Example 7.--This example illustrates the formation of a soluble,relatively high viscosity polymer from a 2:98 mixture of carbon monoxideand ethylene by weight.

A pressure reaction vessel is chargedwith 0.25 part of diethyl dioxideand 100 parts of thisphene-free benzene containing less than 0.01% waterby weight, closed, evacuated, and pressured to 400 atmospheres with amixture of carbon monoxide and ethylene which mixture contains 2% carbonmonoxide by weight. The temperature of the agitated reaction mixture israised to 130 C. and maintained at 128to 136 C. for a period of 17.5hours during which the pressure is kept at 800 to 985 atmospheres byoccasional repressuring with the mixture of ethylene and carbonmonoxide. The vessel is cooled, the excess gases are bled OE, and thevessel is opened. The polymer is milled (in hot The yield of dry polymeris 66 parts. The mol ratio of ethylene to carbon monoxide in the polymeris 20:1 and its intrinsic viscosity is 1.08 (determined in xylene at 85C. and a concentration of 0.125 g. per 100 ml. of solution). A filmpressed from the polymer between smooth surfaces at 140 C. istransparent and has a tensile strength of 1230 lbs. per sq. in. with anelongation at break of 390%. The specimens used in the tensile strengthtest become oriented (i. e. strengthened in the direction parallel tothe direction of the stress) as they are drawn out.

Example 8.-This example illustrates the preparation of a highlyorientable polymer from a 1:199 mixture of carbon monoxide and ethyleneby weight.

A pressure reaction vessel is charged with 0.1 part of diethyl dioxideand 100 parts of thiophene-free, anhydrous benzene, closed, evacuated,and pressured to 250 atmospheres with a mixture of carbon monoxide andethylene which mixture contains 0.5% carbon monoxide by weight. Thetemperature of the agitated reaction mixture is raised to 125C. andmaintained at 123 to 130 C. for a period of 16 hours during which thepressure is kept at 650 to 750 atmospheres by occasional repressuringwith the mixture of carbon monoxide and ethylene The vessel is cooled,bled of excess gases, and opened. The polymer is milled on hot rubberrolls to remove the benzene. The yield of dry polymer is 61 parts. Theinfrared absorption spectrum of the polymer indicates a carbon monoxidecontent of about 1%. A film pressed from the polymer between smoothsurfaces at 160 C. is transparent and has a tensile strength of 2880lbs. per sq. inch with an elongation at break of 590%. The intrinsicviscosity of the polymer (determined in xylene at C. at a concentrationof 0.125 g./ ml. of solution) is 1.12 and its melting point is 210 0.Films cast from a 20% solution of the polymer in hot xylene and cooledrapidly after evaporation of the solvent at C. are clear and have hightear strength. Yarn spun from the xylene solution of the polymer ishighly oriented by cold drawing and is colored more deeply by celluloseacetate type dyes than is polyethylene yarn.

Example 9.-This example illustrates the polymerization of carbonmonoxide and ethylene in a medium comprising both dioxan and benzene.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxide,50 parts of thiophenefree benzene, and 50 parts of dioxan, closed,evacuated, and pressured to 275 atmospheres with a mixture of carbonmonoxide and ethylene which mixture contains 30% carbon monoxide byweight. The temperature of the agitated reaction mixture is raised to C.and. maintained at 129 to C. for a period of 3.5 hours during which thepressure is kept at 600 to 760 atmospheres by occasional repressuringwith the mixture of ethylene and carbon monoxide. The reaction vessel iscooled, the excess gases are bled oil, and the vessel is opened. Thepolymer ismilled on hot rubber rolls to remove the dioxan and benzene.The yield of dry polymer is 44 parts. The mol ratio of ethylene tocarbon monoxide in the polymer is 1.3:1. It is completely soluble inchloroform and hot dioxan and has an intrinsic viscosity of 0.30(determined at 25 C. in chloroform at a concentration of 0.1 g./100 ml.of solution). It reacts readily with hydroxylamine to form a polyoxime,and with formamide and formic acid to form a soluble nitrogen-containingproduct. It also reacts readily with ethane-dithiol in dioxan containinganhydrous hydrogen chloride to form a sulfurcontaining derivative,presumably a dithiolane. The polymer also reacts readily withformaldehyde under alkaline conditions to form a soluble methylolderivative which when heated with an acid catalyst becomes hard, brittleand insoluble and is thus useful as a basis for thermosetting moldingpowders.

Example 10.This example illustrates the preparation of an orientablepolymer from carbon monoxide, ethylene, and propylene with benzoylperoxide as catalyst.

A pressure reaction vessel is charged with 0.5 part of benzoyl peroxide,closed, and evacuated. Then 53 parts of propylene is added and thevessel is pressured to atmospheres with ethylene and then to 500atmospheres with carbon monoxide. The temperature of the agitatedreaction mixture is raised to 75 C. and maintained at 73 C. to 77 C. fora period of 10 hours during which the pressure is kept at 760 to 375atmospheres A casional repressuring with carbon mo xide. The vessel iscooled, the excess gases are bl d off, and the vessel is opened. Theresulting 8% parts of polymer is milled on hot rubber rolls. Itsintrinsic viscosity (determined at C. in chloroform at a concentrationof 0.1 g. /l00 ml. oi. solution) is 0.37 and its carbon monoxide contentis 43% by weight. It melts at 105 C. A film pressed at elevatedtemperatures between smooth surfaces has a tensile strength of 1870 lbs.per sq. inch with an elongation at break of 32%. A sample of the filmbecomes oriented when it is rolled between cold rolls to twice isoriginal length.

Example 11 .--This example illustrates the preparation of an elastomericpolymer of carbon monoxide, ethylene, and propylene with diethyl dieoxide as catalyst.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxideand 100 parts of thiophene-free benzene, closed, and evacuated. Then 43parts of propylene is added and the vessel is pressured to 300atmospheres with a mixture of ethylene and carbon monoxide which mixturecontains carbon monoxide by weight. The temperature of the agitatedreaction mixture is raised to 130 C. and maintained at 129 to 134 C. fora period of 16.5 hours during which the pressure is kept at 860 to 1000atmospheres by occasional repressuring with the mixture of ethylene andcarbon monoxide. The vessel is cooled, the excess gases are bled off.and the vessel is opened. The polymer, yield 26 parts, is milled on warmrubber rolls to remove the benzene. At

room temperature on the rubber rolls it behaves 1 much like rubber. Itcontains 41% carbon monoxide by weight, and the presence of ropylene asa polymer component is apparent from its infra-red absorption spectrum.Its intrinsic viscosity (determined at 25 C. in chloroform at aconcentration of 0.1 -g./100 ml. of solution) is 0.56 and its meltingpoint is 172 C. A film pressed from the polymer at C. between smoothsurfaces is transparent and pliable (bending modulus equals 900 lbs. persq. inch with an elongation at break of 210%.) The elastic recovery of asample of the film is 77% from a stretch of 200%.

Example 12.-This example illustrates the prep? aration of a polymer ofcarbon monoxide, ethylene, and isobutylene.

A pressure reaction vessel is charged with 0.5

, part of diethyl dioxide and parts of thiophenefree benzene, closed andevacuated. Then 22 parts of isobutylene is added and the vessel ispressured to 450 atmospheres with a mixture of carbon monoxide andethylene which mixture contains 30% carbon monoxide by weight. The

- temperature of the agitated reaction mixture is raised to 130 C. andmaintained at 130 to 132 C. for a period of 17 hours during which thepressure is kept at 850 to 1000 atmospheres by occasional repressuringwith the mixture of ethylene and carbon monoxide. The vessel is cooled,the excess gases are bled off, and the vessel is opened. The polymer,yield 22 parts, is milled on warm rubber rolls to remove the benzene. Itcontains 39% carbon monoxide 'by weight and the presence of isobutyleneas a polymer component is apparent from its infrared absorptionspectrum. The intrinsic viscosity of the polymer is 0.55 (determined at25 C. in chloroform at a concentration of 0.1 g./100 ml. of solution)and its melting point is 128 C. It forms a clear solution in chloroform.A film cast from the solution on a glass plate is smooth, clear and'colorless. A film pressed at '110 C. between smooth surfaces is clearand has a tensile strength of 1900 lbs. per sq. inch with an elongationat break of 364%.

Example 13.--This example illustrates the preparation of a polymer ofcarbon monoxide, ethylene, and butadiene.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxideand 100 parts of thiophenefree benzene, closed, and evacuated. Then 13parts of butadiene is added and the vessel is pressured to 450atmospheres with a mixture of carbon monoxide and ethylene which mixturecontains 30% carbon monoxide by weight. The temperature of the agitatedreaction mixture is raised to 130 C. and maintained at 126 to 131 C. fora period of 17 hours during which the pressure is kept at 940 to 1000atmospheres by occasional repressuring with the mixture of ethylene andcarbon monoxide. The vessel is opened. The reaction mixture is filteredthrough cheesecloth to remove the clear insoluble gel which amounts to 3parts. After the benzene is removed from the clear filtrate in a currentof nitrogen, there remains two parts of a clear colorless oil which issoluble in chloroform. Its iodine number is 210. Its composition,calculated from this value and its carbon and hydrogen content is 13carbon monoxide, 37% ethylene, and 50% butadiene by weight. Films caston glass from a benzene solution of this polymer dry in two days at roomtemperature or in 1 hour at C. to hard, tack-free, tough, colorlessfilms without use of metallic driers.

Example 14.-This example illustrates the preparation of a polymer ofcarbon monoxide, ethylene, and diallyl phthalate.

A pressure reaction vessel is charged with 0.5

part of diethyl dioxide, 10 parts of diallyl phthalate, 50 parts ofdioxan, and 50 parts of thiophenefree benzene, closed, evacuated andpressured to 300 "atmospheres with a mixture of ethylene and carbonmonoxide which mixture contains 30% carbon monoxide by weight. Thetemperature of the agitated reaction mixture is raised to 130 C. andmaintained at 128 to 131 C. for a period of 4.5 hours during which thepressure is kept at 600 to 700 atmospheres by occasional repressuringwith the mixture of carbon monoxide and ethylene. The vessel is cooled,the excess gases are bled off, and the vessel is opened. The polymer,yield 24 parts, is freed of benzene, dioxan,

and unreacted diallyl phthalate by distillation of these volatilematerials with steam. The polymer is spongy in form, infusible, andinsoluble in acetone, chloroform, and dioxan.

Example 15.--This example illustrates the preparation of a polymer ofcarbon monoxide, ethylene, and vinyl acetate.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxide,20 parts of vinyl acetate, 50 parts of dioxan, and 50 parts ofthiophene-free benzene, closed, evacuated, and pressured to 250atmospheres with a mixture of carbon monoxide and ethylene which mixturecontains 30% carbon monoxide by weight. The temperature of the agitatedreaction mixture is raised to 130 C. and maintained at 127 to C. for aperiod of 5.5 hours during which the pressure is kept at 600 to 700atmospheres by occasional repressuring with the mixture of ethylene andcarbon monoxide. The vessel is cooled; the excess gases are bled off,and the vessel is opened. The polymer, yield 60 parts, is milled on warmrubber rolls to remove dioxan, benzene. and unreacted vinyl acetate.Its, composition is 37% carbon monoxide,

52% ethylene, and 11% vinyl acetate by weight. Its intrinsic viscosity(determined at 25 C. in chloroform at a concentration 0.1 g./100 ml. ofsolution) is 0.33 and its melting point is 115 C. A film pressed fromthe polymer at 100 C. between smooth surfaces is clear and fairlypliable and has a tensile strength of 1760 lbs. per sq. inch with anelongation at break of 80%.

Example 16.-This example illustrates the preparation of a polymer ofcarbon monoxide, ethylene, and diethyl maleate.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxide,10 parts of diethyl maleate, and 100 parts of dioxan, closed, evacuated,and pressured to 250 atmospheres with a mixture of carbon monoxide andethylene which mixture contains 30% carbon monoxide by weight. Thetemperature ofthe agitated reaction mixture is raised to 130 C. andmaintained at 129 to 142 C. for a period of 3 hours during which thepressure is kept at 500 to 700 atmospheres by occasional repressuringwith the mixture of carbon monoxide and ethylene. The vessel is cooled,excess gases are bled oil, and the vessel is opened. The polymer, yield32 parts, is freed of dioxan and unreacted diethyl maleate bydistillation of these volatile materials with steam. It is then dried bymilling on warm rubber rolls. It is quite pliable and somewhat rubbery.-Its intrinsic viscosity (determined at 25 C. in chloroform at aconcentration of 0.1 g./100 ml. of solution) is 0.23 and its compositionis 39% carbon monoxide, 45% ethylene, and 16% diethyl maleate by weight.A carbon monoxide/ethylene/diethyl maleate polymer prepared in a similarmanner in benzene is tougher and much more rubbery.

Example 17.This example illustrates the preparation of a polymer ofcarbon monoxide, ethylene, vinyl acetate, and diethyl maleate.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxide,10 parts of vinyl acetate, 10 parts of diethyl maleate, 50 parts ofdioxan, and 50 parts of thiophene-free benzene, closed, evacuated, andpressured to 250 atmospheres with a mixture of carbon monoxide andethylene which mixture contains 30% carbon monoxide by weight. Thetemperature of the agitated reaction mixture is raised to 130 C. andmaintained at 128 to 130 C. for a period of 5 hours during which thepressure is kept at 600 to 700 atmospheres by occasional repressuringwith the mixture of carbon monoxide and ethylene. The vessel is cooled,the excess gases are bled-oil, and the vessel is opened. The solventsand unreacted monomers are removed from the polymer by distillation withsteam and the polymer, yield 18 parts, is dried by milling on warmrubber rolls. Its intrinsic viscosity (determined at 25 C. in chloroformat a concentration of 0.1 g./100 ml. of solution) is 0.67 and itsmelting point is 110 C. It contains 43% carbon monoxide and 50% ethyleneand has a saponification number of 48. A film of the polymer pressed at70 C. between smooth surfaces is very pliable and quite rubbery and hasa tensile strength of 250 lbs. per sq. inch with an elongation at breakof 250%. Treatment of the polymer in a hot aqueous dioxan solution withan excess of methanolic potassium hydroxide over the amount required forcomplete hydrolysis, followed by acidification, provides analkali-soluble polyacid which softens at 50 C. to 60 C. and sets up at160 C. in minutes to form a hard, insoluble, infusible product.

Example 18.-This example illustrates the 12 preparation of a'polymer ofcarbon monoxide and vinyl acetate.

A pressure reaction vessel is charged with 0.5 part of benzoyl peroxide,1 part of sodium bisulfite, 50 parts 01' water, and 50 parts of freshlydistilled vinyl acetate, closed, evacuated to about 100 mm., andpressured to 135 atmospheres with carbon monoxide. The temperature ofthe agitated reaction mixture is raised to C. and maintained at 74 to 76C. for a period of 8.5 hours during which the pressure is kept at 120 to125 atmospheres by occasional repressuring with carbon monoxide. Thevessel is cooled, the excess gas is bled off, and the vessel is opened.The unreacted vinyl acetate is removed by steam distillation and theproduct is washed with water and dried. There is thus obtained 26 partsof a hard, brittle polymer which melts at to C. and has an intrinsicviscosity of 0.24 (determined in xylene at 85 C. at a concentration of0.125 g./ ml. of solution). The mol ratio of carbon monoxide to vinylacetate in the polymer is 114.4.

Example 19.-This. example illustrates the preparation of a polymer ofcarbon monoxide and tetra fluoroethylene.

A pressure reaction vessel is charged with 100 parts of oxygen-freewater, 36 parts of isooctane, and 0.2 part of benzoyl peroxide, thecharge occupying about 37.5% of the volume of the reaction vessel. ThepH of the mixture is adjusted to 3.0 with dilute formic acid. Theloading is conducted under a blanket of nitrogen in order to excludeatmospheric oxygen. The reaction vessel is then closed, 200 parts oftetrafluoroethylene is added as a liquid under pressure, and carbonmonoxide is admitted to a total pressure of 400 atmospheres. Thereaction vessel is agitated and heated to 80 C. for 7.75 hours. Thereaction pressure is maintained at 450 to 500 atmospheres by theoccasional admission of more carbon monoxide. At the end of this timethe reaction vessel is cooled and opened, and the contents aredischarged. The product, isolated by steam distillation followed byfiltration and drying, is obtained as a heavy white granular powder.Itcontains 67.7% fluorine, corresponding to 2.3 units oftetrafluoroethylene for each unit of carbon monoxide. Infraredabsorption measurements confirm the presence of carbonyl groups. Thepolymer softens at about 275 C. and at 300 C. melts to a mobile liquidwhich solidifies on cooling to a brittle wax-like solid. It is insolublein hot acetic acid, pyridine, nitrobenzene, toluene, chloroform, andformamide, and is not attacked by nitric or sulfuric acids.

Example 20.This example illustrates the preparation of a polymer ofcarbon monoxide and vinyl chloride.

A pressure reaction vessel is charged with 0.5 part of benzoyl peroxide,100 parts of water, and 1 part of sodium bisulfite, closed, andevacuated. Then 50 parts of vinyl chloride is added and the vessel ispressured to 350 atmospheres with carbon monoxide. The temperature ofthe agitated reaction mixture is raised to 75 C. and maintained at 72 to76 C. for a period of 9.5 hours during which the pressure is kept at 530to 550 atmospheres by occasional repressuring with carbon monoxide. Thevessel is cooled, bled of excess gases, and opened. The yield ofpolymer, which is collected on a filter and dried, is 3.5 parts. Theproduct is soluble in dioxan, phenol, pyridine, and aqueous sodiumhydroxide. It contains 41.9% carbon and 35% chlorine.

Example 21.This example illustrates the preparation of a polymer ofcarbon monoxide and acrylonitrile.

A pressur reaction vessel is charged with 0.5 part of benzoyl peroxide,100 parts of an aqueous solution containing hydrochloric acid by weight,and 50 parts of freshly distilled acrylonitrile, closed, evacuated, andpressured to 700 atmospheres with carbon monoxide. The temperature ofthe agitated reaction mixture is raised to 75 C. and maintained at 67 to76 for a period of 8 hours during which the pressure is kept at 865 to910 atmospheres by occasional repressuring with carbon monoxide. Thevessel is cooled, bled of excess gases, and opened. The reaction mixtureis subjected to steam distillation to remove hydrochloric acid andunreacted monomer. The polymer, yield 23 parts, is col lected on afilter and dried. It is a white, infusible and insoluble soid whichcontains keto groups anal is swelled by phenol, formamlde, anddimethylformamide. The mol ratio of carbon monoxide to acrylonitrile inthe polymer is 1:30.

Example 22.-This example illustrates the preparation of a polymer ofcarbon monoxide,

and butadiene.

A pressure reaction vessel is charged with 0.5 part of diethyl dioxideand closed. Then 50 parts of butadiene is added and the vessel ispressured to 300 atmospheres with carbon monoxide. The temperature ofthe agitated reaction mixture is raised to 130 C. and maintained at 130t0 '132 C. for a period of 14 hours during which the pressure is kept at850 to 900 atmospheres by occasional repressuring with carbon monoxide..The vessel is cooled, bled of excess gases, and opened. The yield ofrubbery polymer is 23 parts. It contains 18% carbon monoxide by weight.-

Example 23.This example illustrates the preparation of apolymer ofcarbon monoxide and ethylene with atmospheric oxygen as catalyst.

In this example the reaction vessel is neither flushed with nitrogen norevacuated. The vessel is charged with 100 parts of anhydrousthiophenefree benzene, closed, and pressured to 250 atmospheres with' amixture of ethylene and carbon monoxide which mixture contains carbonmonoxide by weight. The temperature of the agitated reaction mixture israised to 200 C. and maintained at 198 to 204 C. for a period of 16.5hours during which the pressure is kept at 870 to 900 atmospheres byoccasional repressuring with the mixture of carbon monoxide andethylene. The reaction vessel is cooled, bled of excess gases, andopened. There is obtained 0.4 part of solid polymer in which the molratio of ethylene to carbon monoxide is 2:1.

Example 24.--This example illustrates the preparation of a polymer ofcarbon monoxide and ethylene in the presence of atmospheric oxygen withdioxan peroxide as catalyst.

In this example the reaction vessel is neither flushed with nitrogen norevacuated. The vessel is charged with 100 parts of dioxan containing0.005% oxygen in peroxide form, closed, and pressured with ethylene to400 atmospheres and then further with carbon monoxide to 500atmospheres. The temperature of the reaction mixture is raised to 150 C.and maintained at 148 to 150 C. for a period of 7.5 hours during whichthe pressure is kept at 800 to 950 atmospheres by occasionalrepressuring with carbon monoxide. The reaction vessel is cooled, bledof excess gases, and opened. The polymer is collected on a filter,

washed with methanol, and dried. The yield of white powdery polymer is20 parts. The mol ratio of ethylene to carbon monoxide in the product is4.2 1.

Example 25.-This example illustrates the preparation of a polymer ofcarbon monoxide, ethylene, and tetrafluoroethylene.

A pressure reaction vessel is charged with 0.3 part of ammoniumperoxydisulfate, parts of oxygen-free water, and 75 parts oftertiary-butyl alcohol and closed. Then 63 parts of tetrafluoroethylene,17 parts of ethylene, and 4 parts of carbon monoxide are added. Thetemperature of the agitated reaction mixture is raised to 60 C. andmaintained at 60 C. for a period of 3.5 hours during which the pressureis kept at 1000 to 1400 lbs. per sq. inch by occasional injection ofoxygen-free water into the reaction vessel. The vessel is cooled, bledof excess gases, and opened. The yield of dry polymer is 35 parts. Thepresence of carbonyl groups in the polymer is apparent from its infraredabsorption spectrum. A film pressed from the polymer at 315 C. betweensmooth surfaces has a tensile strength of 6800 lbs. per sq. inch with anelongation at break of 426%.

Example 26.A steel pressure vessel lined with silver is flushed withnitrogen and charged with 2.38 parts of di(tertiarybutyl) peroxide andparts of cyclohexane. The tube is closed, evacuated, placed in a shakermachine, connected to a reservoir containing ethylene admixed with 44%carbon monoxide. Agitation is started, the temperature brought to 135C., and the pres-sure adjusted to 1125 lbs. per sq. inch by bleeding inethylene/carbon monoxide mixed gas from the reservoir. The reactants aremaintained at 134 to 137 C. under pressure of 900 to 1125 lbs. per sq.inch for 13 hours. The total pressure drop obtained is..2 40 lbs. persq. inch. The reactor is then allowed to cool, opened, the productdischarged and subjected to distillation to remove the cyclohexane.There is thus obtained 16 parts of a viscous liquid ethylene/carbonmonoxide polymer which analyzes 72.04% carbon and 9.83% hydrogen. Fromthese data it may be calculated that the ethylene/ carbon monoxidePolymer contains 31.7% carbon monoxide and 68.3% ethylene.

Example 27.--A pressure-resistant vessel is charged with 2 cc.di(tertiarybu.tyl) peroxide, cc. water, 100 g. propylene, and heatedunder a carbon monoxide pressure of 890 to 1000 atmospheres at atemperature of 133 to 136 C. for about 18 hours. The resulting productis removed from the reaction vessel and the water layer is separatedtherefrom. The liquid organic layer is subjected to the action of steamfor from 3 to 4 hours to remove absorbed propylene. The resultingpolymer is dried under diminished pressure at 100 C. for 4 hours. Theproduct thus obtained is a liquid propylene/carbon monoxide polymer,weight 25 g., analyzing as follows: 74.62% carbon; 10.65% hydrogen;25.6% carbon monoxide; ratio of propylene: carbon monoxide, 1.94:1. Thispolymer has a molecular weight in the range of As illustrated by some ofthe above examples, ethylene/carbon monoxide polymers prepared fromethylene/carbon monoxide gas mixtures containing less than about 47%carbon monoxide by weight contain higher proportions of carbon monoxidethan do the monomer mixtures from which they are prepared. Ethylene/carbon monoxide polymers prepared from ethylene/carbon monoxide gasmixtures containing more than about 47% carbon monoxide by weightcontain lower proportions of carbon monoxide than do the monomermixtures from which they are prepared. Generally an ethylene/carbonmonoxide gas composition containing about 46 to 47% carbon monoxide byweight yields homogeneous ethylene/carbon monoxide polymers of about thesame carbon monoxide content as the monomer mixture. 7

The properties of the carbon monoxide liquid and/or solid polymersprovided by the process of this invention vary widely depending on thepolymer components and the proportions in which they are used, and thenature and amount of the reaction medium used, the reaction temperatureand pressure, and the nature and amount of catalyst employed. Theproducts are useful in a wide variety of applications, includingunsupported films, adhesives, safety glass interlayers, fibers, moldedobjects, plasticizers, protective coatings, etc. They may be compressionor injection molded, melt extruded, or calendered. They may be appliedto porous or nonporous substrata in solution or emulsion form bycasting, brushing, spraying, dipping, etc. In many cases their utilityin specific applications may be enhanced by blending them in solution ormilling them with plasticizers, organic or inorganic fillers, pigments,chemical modifying agents, other organic polymers, etc.

Soluble polymers of carbon monoxide and ethyl- L ene are useful in theform of thin coatings on iron or steel to inhibit corrosion,particularly during outdoor exposure.

Since the carbon monoxide polymers of this invention contain ketonegroups, they can be modified chemically by treatment with a wide varietyof chemical agents which normall react with ketones. Thus, by reactionwith formaldehyde or its derivatives there are obtained methylol ketoncswhich, when molded at elevated temperatures with or without fillers inthe presence of hexamethylenetetramine or acidic catalysts such asphthalic or maleic anhydride or without a catalyst, form hard,insoluble, infusible products.

Soluble products of the reaction of the polyketones of this inventionwith formaldehyde or its derivatives are particularly useful as plywoodadhesives, especially when used with an acidic catalyst such as phthalicor maleic anhydride. By reaction of the polyketones of this inventionwith aerylonitrile there are obtained derivatives which contain nitrilegroups and can be hydrolyzed to polyacids. By treatment under suitableconditions with basic materials, that is, materials whose aqueoussolutions have a pH greater than 7, such as ammonia, amines. sodiumhydroxide,

- potassium hydroxide, sodium carbonate, etc., the

soluble polyketones of this invention may be converted into insolubleproducts. Valuable thermosetting compositions are obtained when thepolyketones of this invention are compounded in the dry state with asolid diamine like meta-phenylenediamine. Oximes are obtained byreaction of the polyketones of this invention with hydroxylamine.Hydrogenation of the polyketones of this invention over suitablecatalysts such as copper chromite, ruthenium oxide, or reduced nickelchloride results in conversion of at least a portion of the ketonegroups to alcoholic hydroxyl groups. Treatment of an olefin/carbonmonoxide polymer containing a relatively high proportion to 50% byweight) of carbon monoxide with boiling acetic anhydride, particularlyin the presence of traces of a strong acid like phosphoric acid, resultsin the formation of polymeric products containing furan groups. When thesoluble polyketones of this invention are heated with about 1% or moreby weight of an organic peroxide like benzoyl peroxide they becomeinsoluble and, in many cases, stronger and more pliable. The temperatureat which they become tacky is also raised by this treatment. Whenolefin/carbon monoxide polymers are treated with a stronger oxidizingagent like hot 70% nitric acid, they are oxidized to dibasic acids whichmay be viscous liquids, greasy solids, or hard waxes and may havemolecular weights as high 'as 2000 or higher. Incomplete oxidation ofolefin/carbon monoxide polymers yields acids containing ketone groups.

Various changes may be made in the methods and preferred embodiments ofthis invention without departing therefrom or sacrificing the advantagesthereof.

I claim:

1. A process for the preparation of polymerization products whichcomprises heating together carbon monoxide with a polymerizable organiccompound containing ethylenic unsaturation in the presence of a per-oxycompound catalyst, and in the absence of a Friedel-Crafts catalyst, saidcompound containing ethylenic unsaturation being one which undergoesaddition polymerization when subjected to the polymerizing action of aper-oxy compound.

2. A process for the preparation of polymerization products whichcomprises heating together carbon monoxide substantially free of metalcarbonyl with an aliphatic monoolefin, in the presence of a per-oxycompound catalyst, and in the absence of a, Friedel-Crafts catalyst, ata temperature between 25 and 350 C.

3. A process for the preparation of polymerization products whichcomprises heating together carbon monoxide and ethylene, in the presenceof a per-oxy compound catalyst, and in the absence of a Friedel-Craftscatalyst, at a, temperature between 25 and 350 C.

4. A normally solid interpolymer of carbon monoxide with an aliphaticmonoolefin.

5. A normally solid orientable polymer of carbon monoxide with analiphatic monoolefin.

6. A normally solid polymer of carbon monoxide with ethylene.

7. A process for preparing polymers which comprises heating carbonmonoxide with at least one peroxide-polymerizable organic compoundcontaining ethylenic unsaturation in the presence of a per-oxy compoundcatalyst in the absence of a, Friedel-Crafts catalyst undersuperatmospheric pressure at a, temperature within the range of 25 to350 C., said compound containing ethylenic unsaturation being one whichundergoes addition polymerization when subjected to the polymerizingaction of a per-oxy compound.

8. A process for preparing polymers which comprises heating carbonmonoxide substantially free of metal carbonyl with a, monoolefin in thepresence of a per-oxy compound catalyst in the absence of aFriedel-Crafts catalyst under superatmospheric pressure at a temperaturewithin the range of 25 to 350 C., separating the resultant polymer fromthe reaction mixture, and thereafter subjecting the said polymer to a,stress whereby it becomes oriented.

9. A process for the preparation of normally solid ethylene/carbonmonoxide interpolymers which comprises heating together carbon monoxideand ethylene in the presence of a per-oxy compound catalyst and in theabsence of a 17 F'riedel-Crafts catalyst under a pressure within therange of 500 to 1500 atmospheres, a a temperature between 25 and 350 C.

10. A normally solid orientable interpolymer of carbon monoxide with apolymerizable organic compound containing ethylenic unsaturation, saidinterpolymer being characterized in that the carbon monoxide is combinedtherein in the form of a plurality of carbonyl groups, said compoundcontaining ethylenic unsaturation being one which undergoes additionpolymerization across the C=C group when subjected to the polymerizingaction of a per-oxy compound.

11. A coated article comprising a base material carrying a protectivecoating containing as an essential ingredient a normally solid polymerof 1 carbon monoxide with ethylene.

12. An interpolymer of carbon monoxide with ethylene, said interpolymerbeing characterized in that it has a polyketone structure.

13. An interpolymer of carbon monoxide with an aliphatic monoolefin,said interpolymer being characterized in that it has a polyketonestrucbore.

14. An interpolymer of carbon monoxide with a polymerizable compoundcontaining ethylenic un saturation, said compound containing ethylenicunsaturation being one which undergoes addition polymerization acrossthe C=C group when subjected to the polymerizing action of a per-oxycompound, said interpolymer being characterized in that it has apolyketone structure.

15. An interpolymer formed from comonomers consisting of carbon monoxideand organic polymerizable comonomer having at least one terminalmethylene group, said interpolymer being characterized in having apolyketone structure.

MERLIN M. BRUBAKER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Name Date 'Kleine June 27, 1944 Number

1. A PROCESS FOR THE PREPARATION OF POLYMERIZATION PRODUCTS WHICHCOMPRISES HEATING TOGETHER CARBON MONOXIDE WITH A POLYMERIZABLE ORGANICCOMPOUND CONTAINING ETHYLENIC UNSATURATION IN THE PRESENCE OF A PER-OXYCOMPOUND CATALYST, AND IN THE ABSENCE OF A FRIEDEL-CRAFTS CATALYST, SAIDCOMPOUND CONTAINING ETHYLENIC UNSATURATION BEING ONE WHICH UNDERGOESADDITION POLYMERIZATION WHEN SUBJECTED TO THE POLYMERIZING ACTION OF APER-OXY COMPOUND.